Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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LITHIUM SECONDARY BATTERY
FIELD OF THE INVENTION
This invention pertains to a lithium secondary battery with good charge-
discharge
cycle characteristics which has low internal resistance, and in particular, to
a battery which
uses a lithium manganese oxide for a positive active material and is intended
for use as a
power source for portable electronic devices, electric vehicle motors, hybrid
electric vehicle
motors, and the like.
BACKGROUND OF THE INVENTION
Reduction in size and weight of portable electronic devices such as portable
telephones, camcorders, and lap top computers has proceeded rapidly in recent
years.
Secondary batteries have come into use for such devices, 'and use a lithium
transition metal
compound as a positive active material, a carbon material as a negative
material, and an
electrolyte which dissolves lithium ion electrolyte in an organic solvent.
Such batteries are generally called lithium secondary (or rechargeable)
batteries or
lithium ion batteries, and due to their great energy density and the fact the
cell voltage is
high at around 4 V, they are attracting attention as power sources for
electric vehicles
(hereinafter referred to as "EV") and hybrid electric vehicles (hereinafter
referred to as
"HEV"). With the present concern over environmental problems, these types of
vehicles are
becoming known to the general public as low pollution vehicles.
The battery capacity and charge-discharge cycle characteristics (hereinafter
referred
to as "cycle characteristics") of lithium secondary batteries like these
depend largely on the
properties of the material used in the positive active material. The lithium
transition metal
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compound uses .a positive active material such as lithium cobalt oxide
(LiCoO,), lithium
nickel oxide (LiNi02), and lithium manganese oxide (LiMnz04).
Of these, LiMn204 is an inexpensive raw material, has high output density, and
can
handle high voltages. However, its discharge capacity decreases gradually with
repeated
charging-discharging cycles, and good cycle characteristics are difficult to
obtain.
However, these disadvantages are being slowly overcome as studies of crystal
structure and
composition have proceeded in recent years.
Regardless of the type of positive active material used in a lithium secondary
battery, reducing the electrical resistance of the positive active material
should reduce the
internal resistance of the battery. That is, improving the conductivity of the
positive active
material is the most important matter from the standpoint of improving the
characteristics of
the battery. Reducing the internal resistance of the battery is very important
in order to
obtain the large current output necessary for EV's and HEV's to accelerate and
climb steep
grades, as well as for improving the charging-discharging efficiency.
As one means of solving this problem in the past, fine conductive particles of
such
materials as acetylene black have been added to the positive active material
to improve
conductivity and reduce the internal resistance of the battery. However, the
addition of
acetylene black is a problem in that it reduces the battery capacity by
reducing the amount
of positive active material that can be used. In addition, since acetylene
black is a type of
carbon and a semiconductor, it is believed that there are limits as to how
much electronic
conductivity will improve. Furthermore, acetylene black is voluminous and is
difficult to
handle in the fabrication of electrode plates. Thus, although adding acetylene
black has the
advantage of reducing internal resistance, it has the disadvantage of reducing
the battery
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capacity. The proper proportion of acetylene black is known in the prior art
due to its ease
of manufacture and comparison with other attempted solutions.
SUMMARY OF THE INVENTION
In accordance with the present invention, a lithium secondary battery uses a
lithium
manganese oxide for a positive active material having a cubic spinet structure
which has a
crystallite size of 58 nm or greater and/or a lattice distortion of 0.09% or
less. The ratio of
Li/Mn in the lithium manganese oxide is preferably greater than 0.5.
In accordance with a preferred method for synthesizing the lithium manganese
oxide, a mixed compound, including salts and/or oxides of each of the
elements, is fired in
an oxidizing atmosphere in a range of 650°C to 1000°C for 5 to
50 hours. The properties of
the resultant crystal are improved by firing two or more times, preferably
with an increase in
firing temperature over the temperature of the previous firing.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the nature and objects of the invention,
reference
should be made to the following detailed description of a preferred mode of
practicing the
invention, read in connection with the accompanying drawings, in which:
Fig. 1 is a graph showing the relationship between crystallite size and
internal
resistance of coin-type cells.
Fig. 2 is a graph showing the relationship between lattice distortion and
internal
resistance of coin-type cells.
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the lithium secondary battery of this invention, lithium manganese oxide
having a
cubic spinet structure is used as positive active material. A stoichiometric
composition of
the lithium manganese oxide having a cubic spinet structure is expressed as
LiMn204, but
this invention is not restricted to this stoichiometric composition and
LiMXMn2_X04, which
substitutes a different element M for a portion of the transition element Mn,
is optionally
used, where "x" represents the quantity of the substitution. When elements
have been
substituted in this fashion, the ratio of Li to Mn, when a portion of Mn is
substituted for Li
and there is an excess, stoichiometrically speaking, of Li, becomes (1 + x)/(2
- x) and when
substituted by an element M other than Li, the ratio becomes 1/(2 - x), so
that preferably the
Li/Mn ratio is >0.5.
Substitution.elements M may be Li, Fe, Mn, Ni, Mg, Zn, B, Al, Co, Cr, Si, Ti,
Sn, P,
V, Sb, Nb, Ta, Mo or W. Among the substitution elements M, Li theoretically is
an ion
which has a valence of +l, Fe, Mn, Ni, Mg and Zn have a valence of +2, B, Al,
Co and Cr
have a valence of +3, Si, Ti and Sn have a valence of +4, P, V, Sb, Nb, and Ta
have a
valence of +5, and Mo and W have a valence of +6. While they are elements in
solid
solution in LiMn204, Co and Sn may have a valence of +2, Fe, Sb and Ti may
have a
valence of +3, Mn may have valences of +3 and +4, and Cr may have valences of
+4 and
+6. Thus, each type of substitution elements M may exist in a state having a
compound
valence and it is not necessary for the quantity of oxygen to be 4 as is
expressed in
theoretical chemical compositions. Within the limits for maintaining crystal
structure, it
does not matter if oxygen is deficient or excessive.
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Thus, in this invention, when using a LiMn204 spinet like this, a crystallite
size of 58
nm or greater is used. As the example of application below shows, when this
condition is
fulfilled, the resistance of the positive active material decreases and the
battery
characteristics improve. Crystallite as used herein refers to microscopically
or ultra-
microscopically small monocrystals and the size thereof is a value that can be
obtained by
analyzing a diffraction pattern obtained by powder X-ray diffraction using the
Wilson
method. More specifically, the crystallite size in this invention is
determined using Rigaku
Denki Ltd.'s RINT 2000 series application software "Crystallite Size and
Lattice
Deformation Analysis," Version 3, October 16, 1996.
When using a LiMn204 spinet, it is preferable to use a material with a lattice
distortion of 0.09% or less. If this condition is also fulfilled, then the
internal resistance of
the battery can be reduced even further. Lattice distortion as used herein
refers to instances
where the lattice is abnormal, i.e., where the crystal lattice is irregular
due to defects in a
portion of the crystal or external force. This lattice distortion can be
determined by using
the Wilson method.
Thus, when the crystallite size and lattice distortion are determined by
another
method of analysis and differ from the value determined by this invention, the
import of this
invention is not influenced by these differences in methods of analysis. When
both the
crystallite size and lattice distortion fulfill the conditions mentioned
earlier, the effect on the
battery characteristics are manifested very strongly and the internal
resistance of the battery
effectively decreases.
The method of synthesizing the LiMnz04 spinet which has the crystallite size
and/or
the lattice distortion described earlier will now be explained. The salts
and/or oxides of
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each element (including the substitution elements M when replacing a portion
of Mn) are
used for the synthesizing material. While there are no restrictions on the
salts or oxides of
each element, it is preferred to use starting materials having a high degree
of purity. Also,
using carbonates, hydroxides and organic acids which do not give off harmful
decomposition gases is preferred. However, nitrates, hydrochlorides, and
sulfates may be
used. With respect to lithium compounds, LizO is preferably not used since it
is chemically
unstable. Optimally, hydroxides and carbonates are used.
These materials, mixed in designated proportions, are initially fired for a
period of 5
to 50 hours at a temperature of 650°C to 1000°C in an oxidizing
atmosphere. "Oxidizing
atmosphere" generally refers to an atmosphere which has oxygen pressure in
which the
specimen in the furnace causes an oxidation reaction, and more specifically,
corresponds to
an atmosphere of air or oxygen.
After this initial firing, the uniformity of composition is not necessarily
good, and
the crystallite size tends to be small with large lattice distortion. However,
when the ratio of
Li/Mn satisfies the condition of being greater than 0.5, i.e., when a portion
of Mn is
substituted by substitution elements, particularly when an excess of Li is
formed by
replacing a portion of Mn with Li and Ti, it has been confirmed by tests that
the crystallite
size and lattice distortion easily satisfy the specified conditions with one
firing. The reason
for this is not clear, but crystal lattice stabilization is sought by adding
substitution elements
M, and it is presumed that the phase atmosphere of synthesis changes due to an
atmosphere
conducive to crystal growth, for example, liquid phase atmosphere or gas phase
atmosphere.
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In this way, the crystallite size and/or lattice distortion related to the
composition
can meet the specified conditions with one firing but it is preferable to
perform a number of
firing steps in order to reduce nonuniformity of the composition for
synthesis. In this case,
it is even more preferable from the standpoint of uniformity of composition to
pulverize
after the first firing and then to perform the second and subsequent firings.
The number of
firings largely depends on the firing temperature and the firing time. When
the firing
temperature is low and/or the firing time is short, many firing steps are
required. From the
standpoint of uniformity of composition, depending on the type of substitution
element M,
there are instances when it is preferable to increase the number of firings.
These are cases
when it is thought to be difficult to have a phase atmosphere suitable to the
growth of the
crystal due to the addition of substitution elements M.
However, since increasing the number of firings means lengthening the
production
process, it is preferable that the number of firings is limited to the minimum
necessary.
With specimens obtained by performing multiple firings, it is possible to
confirm that there
is an improvement in crystallinity over specimens that have been obtained from
one firing
from observing the sharp protrusion of the peak configuration on the XRD
charts.
Pulverization processing is performed after each firing with no limitations on
how it
is done. For example, ball mill, vibrating mill, and air current pulverizing
machines may be
used. Pulverization processing contributes to uniformity of particle size, and
in order to
obtain sufficient uniformity of composition, pulverization processing should
preferably be
performed so that average particle size is 10 ~cm or less. The average
particle size in this
case is obtained by measuring ultrasonically dispersed particles in distilled
water with the
laser diffraction method.
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When the firing temperature is less than 600°C, a peak indicating a
residue of raw
materials is observed on the XRD chart of the fired product. For example, when
lithium
carbonate (LizC03) is used as a source of lithium, a peak for Li2C03 is
observed, and no
single-phase products can be obtained. On the other hand, when the firing
temperature is
greater than 1000°C, a high temperature phase is produced in addition
to the intended
crystal system and a single phase product can no longer be obtained.
As explained above, using the LiMn204 spinel which satisfies the conditions of
this
invention improves the electric conductivity characteristics of the positive
active material as
well as the state of dispersion of fine powders, such as acetylene black,
which are added as
aids to conductivity and internal resistance of the battery. Since this
suppresses the
generation of Joule heat due to the charging-discharging cycle of the battery,
the thermal
load on the active material and electrolyte is lessened, charging and
discharging efficiency
is enhanced, and the cycle characteristics are improved. Thus, the present
invention
suppresses the decrease in battery capacity that occurs over time due to
repeated chargings
and dischargings. It also makes it possible to decrease the amount of
acetylene black used
and other additives.
The reduction of internal resistance, the maintenance of positive capacity,
and the
improvement in cycling characteristics are particularly noticeable in large
capacity batteries
which use large amounts of electrode active material. Thus, it can be used,
for example, for
the power source for EV and HEV motors while maintaining driving performance
for proper
acceleration and climbing steep grades. It also has the effect of enabling
continuous long
distance travel on one charging. This invention is also applicable to low
capacity batteries
such as coin-type batteries, and the like.
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There are no particular restrictions on other materials that may be used in
the
manufacturing of batteries, and various publicly known types of materials used
in the past
may be used. For example, amorphous carbon materials, such as soft carbon and
hard
carbon, and artificial graphite, such as highly graphitized carbon or carbon
materials, which
are natural may be used for the negative active material.
For organic electrolytes, one or more types of lithium fluoride complex
compounds
such as LiPFb and LiBF4, lithium halogenides such as LiC104, electrolytes
dissolved in
carbonic esters such as ethylene carbonate (EC), diethytcarbonate (DEC),
dimethylcarbonate, propylene carbonate (PC), a single solvent or compound
solvents of
organic solvents such as 'y-butyrolactone, tetrahydrofuran, and acetonitrile,
etc. may be
used.
Exam lies
For the synthesis of positive active material LiMn204 spinet, commercially
available
Li2C03 and MnOz powders were used for the starting raw materials. The raw
materials
were weighed and mixed to provide the compositions shown in Examples 1-10 and
Comparative Examples 1 and 2 in Table 1, and then fired in an oxidizing
atmosphere (air)
under the conditions of the first firing conditions as noted in Table 1.
Samples of the
powder obtained from the first firing of Comparative Examples 1 and 2 and
Example 10
were taken. In contrast, material from Examples 1-9 were subjected to
pulverization
processing after the first firing to a mean particle size of 10 ,um or less,
fired for a second
time under the conditions shown in Table 1, and samples taken.
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Table 1
Specimen CompositionFirst Firing Second Firing
Conditions Conditions
Example 1 LiMn204 650C 10 hours 800C 24 hours
Example 2 LiMn204 650C 10 hours 900C 24 hours
Example 3 Li,.,Mn,.904650C 10 hours 800C 24 hours
Example 4 Li,.,Mn,,904650C 10 hours 900C 24 hours
Example 5 Li,.,Mn,.904650C 10 hours 950C 24 hours
Example 6 LiMnz04 650C 10 hours 1000C 24 hours
Example 7 LiMn204 650C 10 hours 700C 24 hours
Example 8 Li,_,Mn,.904650C 10 hours 1000C 24 hours
Example 9 Li,.,Mn,,904650C 10 hours 700C 24 hours
Example 10 Li,.,Mn,,904800C 24 hours None
Comparative ExampleLiMnz04 800C 24 hours None
1
Comparative ExampleLiMn204 850C 24 hours None
2
Crystallite size and lattice distortion of each of the specimens obtained were
measured using an X-ray diffraction device having a rotating anode type target
(Cu) and a
graphite monochrometer (RINT 250 made by Rigaku Denki), with the powder X-ray
diffraction method (XRD) with a gonio radius of 185 mm, a divergent slit (DS)
of 1/2°, a
scattering slit (SS) of 1/2°, and a receiving slit (RS) of 0.15 mm. The
crystallite size and
lattice distortion were determined using the Wilson method from the peak
position of
LiMn204 spinet appearing at diffraction angle 28 = 10° to 70°
under conditions of 50 kV
and 300 mA using Cu Ka rays as the X ray source. For determination of peak
position and ,
apparatus function, Si monocrystal (SRM640b) was used as an internal standard
specimen.
Batteries were prepared as follows. Acetylene black powder, the conductive
material, and polyvinylidene fluoride, the binding agent, were mixed in
proportions of
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50:2:3 (by weight) to prepare the positive material for each type of specimen
prepared. An
amount of 0.02 g of the positive material was press formed at 300 kg/cmz into
a coin shape
having a diameter of 20 mm and made into a positive electrode. A coin-type
cell was
prepared using this positive electrode, having a battery electrolyte prepared
by dissolving an
electrolyte of LiPFb dissolved in an organic solvent mixed with equal volumes
of ethylene
carbonate and diethycarbonate so that it would be a concentration of 1 mol/L,
a negative
electrode of carbon, and a separator separating the positive and negative
electrodes.
The internal resistance of the cell prepared as described above was measured
by
conducting one charge-discharge cycle by charging at a constant current of 1
Coulomb and
constant voltage of 4.1 V in accordance with the capacity of the positive
active material and
similarly discharging at a constant current of 1 Coulomb to 2.5 V, and
dividing the
difference (difference in electrical potential) between the potential at a
resting state after
finishing charging and the potential immediately after commencement of
discharging by the
discharging current.
The relationship between the internal resistance of the cell and crystallite
size is
shown in Fig. 1. The relationship between the internal resistance of the cell
and lattice
distortion is shown in Fig. 2. In Examples 6 and 8, while the crystallite size
is 58 nm or
greater, lattice distortion is 0.1 % or greater. It is believed that crystal
growth was
accelerated by raising the firing temperature while conversely making it easy
for defects to
occur and the lattice distortion increased. In contrast, in Examples 7 and 9,
lattice distortion
was smaller than 0.09% while crystallite size was 55 nm or less. In this case,
in contrast to
Examples 6 and 8, it is believed that as the firing temperature was low, it
was harder for
defects to occur rather than the crystal growth being suppressed.
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However, since the internal resistance of the cells is low in Examples 6
through 9
compared with Comparative Examples 1 and 2, it was confirmed that the
resistance in the
battery decreased either through the crystallite size or the lattice
distortion fulfilling the
specified conditions.
In addition, it is clear from Fig. 1 that crystallite size is 58 nm or greater
and also
clear from Fig. 2 that lattice distortion is 0.09% or less with the LiMnz04
spinel prepared by
two firings in Examples 1-5 regardless of the composition of the LiMnz04
spinet,
confirming that the internal resistance of the cell decreased. In other words,
it is clear that
when crystallite size and lattice distortion have specified values, it is
possible to make
batteries with low internal resistance, the same as when at least either the
crystallite size or
the lattice distortion fulfill specified conditions.
In contrast to Examples 1-9, when both the crystallite size and lattice
distortion do
not fulfill the specified conditions, in other words, in Comparative Examples
l and 2, it was
confirmed that the internal resistance of the cell increased. In Example 10,
crystallite size
was 58 nm and lattice distortion was 0.09%, both values being the border
values prescribed
by this invention and a low resistance cell was obtained despite just one
firing. While this is
thought to be due to the effect of the composition of Example 10, by firing
Examples 3-5
twice, which had the same composition as Example 10, within the appropriate
temperature
ranges it was possible to achieve preferred values for crystallite size and
lattice distortion
which deviated from the border values.
As described above, the superior result of reduction of the internal
resistance of
batteries can be achieved, and as a result, charging-discharging efficiency
and cycle
characteristics can be improved with the lithium secondary battery of this
invention by
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using low resistance LiMn204 spinet whose electric conductivity has been
improved as a
positive active material. In addition, the amount of conductivity enhancing
additives can be
reduced, leading to improvements in battery capacity and energy density.
While the present invention has been described with reference to a particular
preferred embodiment and the accompanying drawings, it will be understood by
those
skilled in the art that the invention is not limited to the preferred
embodiment and that
various modifications and the like could be made thereto without departing
from the scope
of the invention as defined in the following claims.
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